Patent GB-692261-A (GB)
Title: Organic phosphorus compounds and compositions of matter containing such compounds
IPC: C21D1/58
Filed: 1950-02-21
Abstract: Phosphorus- and halogen-containing organic products suitable for use as additives for lubricants and other vehicles (see Groups III and V) are obtained by reacting at elevated temperature an organo phosphite as defined below with an organic halogen-containing phosphonate as defined below.  The term organo phosphite is defined as a compound of one of the following classes: (a) triesters of phosphorus acid, (b) metal or organic base salts of diesters of phosphorous acid, (c) compounds as in (a) and (b) in which one or more of the oxygen atoms attached to the phosphorus atom have been replaced by sulphur, selenium or tellurium atoms; whilst the term organic halogen-containing phosphonate is defined as a compound of one of the following classes: (a) diesters of phosphonic acids of the general formula R.PX.(XH)2 in which X represents an oxygen, sulphur, selenium, or tellurium atom and R is a saturated or unsaturated organic radical bonded to the phosphorus atom through one of its carbon atoms and which radical contains either at least one halogen atom not more than four carbon atoms removed from the phosphorus atom or three halogen atoms attached to a terminal carbon atom, (b) metal or organic base salts of phosphonic acids of the above general formula, (c) metal or organic base salts of monoesters of phosphonic acids of the above general formula.  The ester radicals of both the organo phosphites and the organic halogen-containing phosphonates may be saturated or unsaturated radicals and are preferably hydrocarbon radicals.  They may, however, be substituted by polar groups such as OH, Cl, SH, SO3H, NH2, NO and N : NO.  The halogen-containing phosphonates of type (a) may be prepared by reacting at elevated temperature an organophosphite as defined above with a polyhalogenated organic compound of the formula RD wherein R is a halogenated organic radical bonded to a halogen atom D, which radical contains either at least one halogen atom not more than four carbon aroms removed from D or three halogen atoms attached to a terminal carbon atom.  The resulting diesters may be further reacted by known processes to yield organic halogen-containing phosphonates of the types (b) and (c) above.  When the organophosphite or phosphonate is a salt it may be an alkylamine or an alkylolamine salt or a salt of a monovalent or polyvalent metal, e.g. lithium, sodium, potassium, rubidium or caesium; calcium, strontium, barium, beryllium, magnesium, zinc, cadmium, aluminium, gallium, indium, thallium, titanium, zirconium, tin, lead, bismuth, chromium, molybdenum, manganese, iron, cobalt, or nickel.  The ester radicals in the organophosphites and in the organic halogen-containing phosphonates may be saturated or unsaturated and, when the compound contains more than one ester radical, they may be the same or different radicals. The radicals may be alkyl, aryl, cycloalkyl, alkylaryl, alkylated cycloalkyl, cycloalkylated aryl or arylated cycloalkyl radicals. Several such radicals are specified including methyl, ethyl, octadecyl, allyl, oleyl, methoxyphenyl, octoxyphenyl, dichlorohexoxy phenyl, thiomethoxyphenyl, selenomethoxyphenyl, telluromethoxyphenyl, acetylphenyl, lanoylphenyl, stearoylphenyl, stearoylethyl and lauroylethyl.  A list of organo phosphites suitable as starting materials is given and it is stated that the di- and tri-ethly phosphites, the di- and tri-butyl phosphites, the di- and tri-amyl phosphites, the di-and tri-phenyl phosphites, and the corresponding di- and tri-thiophosphites are preferred, the diesters when used for reaction with the polyhalogenated compound RD being used in the form of the metal or organic base salt.  A list of polyhalogenated organic compounds which can be used to produce the organic halogen-containing phosphonates is also given and this includes carbon tetrachloride, bromoform, iodoform, methylene chloroiodide, hexachloroethane, methylene fluoride; the polyhalogenated fatty acids in which the halo radicals are preferably attached in the alpha or beta position to the carboxyl group, e.g. dichloroacetic acid, alpha, alpha, beta-trichlorobutyric acid and beta, beta-dibromopropionic acid; and polyhalogenated aldehydes, ketones and ethers such as chloral, bromal, trichlorobutanone, polychloromethyl isobutyl ketone and the dichloroethyl ethers.  In examples: (1) triethyl phosphite is refluxed with dry carbon tetrachloride and the diethyl trichloromethanephosphonate formed is then heated with triethyl phosphite in an inert atmosphere to yield a viscous liquid product soluble in mineral and synthetic oils; (2) tributyl phosphite is refluxed with carbon tetrachloride and the di-n-butyl-trichloromethanephosphonate formed is then heated under nitrogen with tributyl phosphite; (3) di-n-butyl trichloromethane phosphonate is reacted under nitrogen with tri-sec.-butyl phosphite; (4) tri-sec.-butyl phosphite is refluxed with carbon tetrachloride and the resulting phosphonate then reacted under nitrogen at 100 DEG to 200 DEG  C. with tri-sec.-butyl phosphite; (5) di-sec.-butyltrichloromethane phosphonate is reacted under nitrogen with tri-n-butyl phosphite; (6) tributyl phosphite is heated with 1-bromo-3-chloropropane and the dibutyl - 3 - chloropropane - 1 - phosphonate obtained is then reacted with tributyl phosphite under nitrogen at 100 DEG  to 200 DEG  C.; (7) ethyl trichloroacetate is heated with triethyl phosphite and the product then reacted under nitrogen with tributyl phosphite at 100 DEG  to 200 DEG  C.; (8) tributyl phosphite is reacted at 155 DEG  C. with sym.-dichlorodiethyl ether and the resulting phosphonate is then reacted with tributyl phosphite under nitrogen at 100 DEG  to 200 DEG C. It is stated that other reaction products may be obtained by reacting diethyl sodium phosphite with carbon tetrachloride and reacting the phosphonate product with diethyl sodium phosphite; and by reacting diethyl potassium phosphite with the halogen - containing phosphonate obtained by reacting the following pairs of reactants:-diethyl potassium phosphite and chloroform; diethyl sodum phosphite (or tributyl phosphite) and trichloroacetic acid; triamyl phosphite and chloral; tricyclohexyl phosphite and chloroform (or carbon tetrachloride or trichloroacetic acid); amyl phenoxyethyl lithium phosphite and carbon tetrachloride; triethyl trithiophosphite (or tricresyl thiophosphite) and carbon tetrachloride; triethyl trithiophosphite and trichloroacetic acid (or chloral); tricyclohexyl trithiophosphite (or triethyl mono-selenophosphite) and carbon tetrachloride; tricresyl dithiophosphite and hexachloroethane; sodium diethyldithiophosphite and bromoform; triamyl monothiophosphite and carbon tetrabromide; triallyl phosphite and carbon tetrachloride. The reaction products of the invention may be converted into salts by treating them with organic bases, e.g. amines, or with metal oxides, hydroxides or carbonates.  The Na, Li, K, Cu, Ba, Sr, Mg, Zn, Al, Cr, Co and Ni salts are preferred. The reaction products may be added to a substantially neutral liquid or solid medium which may be weakly acidic or basic, preferably having a dissociation constant not above 10-8, for improving the lubricating qualities of said vehicles (see Group III), for producing corrosion protective compositions, biocidal compositions or compositions exhibiting flame retarding properties. Both polar and non-polar vehicles may be employed. Among the former are water, monohydric alcohols, polyhydric alcohols, phenols (including alkyl phenols) and thiophenols, ketones, keto alcohols, ethers, neutral esters of carboxylic and other acids, fats and natural waxes (see Group III), and several such vehicles are specified.  The vehicles may also comprise hydrocarbons (several specified), aromatic solvents boiling between 200-550 DEG  F., or resinous materials such as petroleum resins, natural resins such as rosin, resins formed by polymerization of drying fatty oils, phenol formaldehyde resins and glyptal type resins formed by esterification of polyhydric alcohols with polycarboxylic acids.  The compositions may also include antioxidants, e.g. alkyl phenols (several specified), aminophenols, such as benzylaminophenols, or amines such as dibutyl-phenylene-diamine, diphenylamine, phenyl-beta (or alpha-)-naphthylamine and dinaphthylamine.  Corrosion inhibitors or anti-rusting compounds may also be present, e.g. dicarboxylic acids of 16 or more carbon atoms, alkali metal and alkaline earth metal salts of sulphonic acids and fatty acids and organic compounds containing an acidic radical in close proximity to a nitrile, nitro, or nitroso group, e.g. alpha cyanostearic acid, whilst additional ingredients may comprise oil-soluble urea or thiourea derivatives, e.g. urethanes, allophanates, carbazides, carbazones, polyisobutylene, and unsaturated polymerized esters of fatty acids and monohydric alcohols.ALSO:A composition of matter comprises a substantially neutral liquid or solid medium and a minor proportion by weight of a product obtainable by reacting at elevated temperature an organo phosphite as defined below with an organic halogen-containing phosphonate as defined below.  The organo phosphite is defined as a compound of one of the following classes:-(a) triesters of phosphorus acid, (b) metal or organic base salts of diesters of phosphorous acid, (c) compounds as in (a) and (b) in which one or more of the oxygen atoms attached to the phosphorus atom have been replaced by sulphur, selenium or tellurium atoms; whilst the term organic halogen-containing phosphonate is defined as a compound of one of the following classes:-(a) diesters of phosphonic acids of the general formula RPX(XH)2 in which X represents an oxygen, sulphur, selenium, or tellurium atom and R is a saturated or unsaturated organic radical bonded to the phosphorus atom through one of its carbon atoms and which radical contains at